CN1554692A - Process for microwave radiation synthesizing cellulose base high water absorption resin - Google Patents
Process for microwave radiation synthesizing cellulose base high water absorption resin Download PDFInfo
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- CN1554692A CN1554692A CNA2003101077731A CN200310107773A CN1554692A CN 1554692 A CN1554692 A CN 1554692A CN A2003101077731 A CNA2003101077731 A CN A2003101077731A CN 200310107773 A CN200310107773 A CN 200310107773A CN 1554692 A CN1554692 A CN 1554692A
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Abstract
The microwave radiation process of synthesizing cellulose-base resin with high water absorption includes the following steps: moistening cellulose with deionized water, gelatinizing under microwave radiation, adding potassium persulfate or potassium permanganate and sodium thiosulfate or sodium sulfite oxidation-reduction initiating system and microwave radiating to initiate the reaction for 4-7 min; adding successively the crosslinking agents N,N-methyene-bisacrylamide, epoxy chloropropane or polyglycol bisacrylate, acrylamide or propenyl sodium sulfonate and acrylic acid or methyl acrylic acid, regulating neutralizing degree to 65-75%, reaction under stirring and microwave radiation for 7-10 min, soaking the produced white matterin methanol for 3-5 hr, stoving and crushing. The present invention completes the grafting copolymerization of cellulose in only ten-odd min, and jas high production efficiency and other advantages.
Description
Technical field: the preparation method who the present invention relates to a kind of High hydrophilous resin.
Background technology: High hydrophilous resin belongs to new functional macromolecule material, it can absorb and keep the water of own wt hundred times even thousands of times, have peculiar suction and water retention capacity, be widely used in especially in health-care industry, occupying unique status and wide application market in industrial and agricultural production, gardening plantation and the daily life.Super absorbent resin can be divided three classes by raw material sources: synthesizing series, starch base series and cellulose base series.Mostly last class be with slight crosslinked the making of acrylate, and back two classes are to be substrate with starch or Mierocrystalline cellulose, and hydrophilic vinyl monomer is arranged after wetting ability or the hydrolysis in the graft copolymerization.Suitability for industrialized production is many based on synthesizing series, because reaction is easy to realize and water-intake rate is higher, but the resin residue vinylformic acid that this method makes is unfavorable for HUMAN HEALTH, and this resinoid is difficult for being belonged to the non-ambient friendly materials by biological degradation; Super absorbent resin suction and water retention that starch graft copolymer is produced are strong, also have been used for suitability for industrialized production; Because the Mierocrystalline cellulose wide material sources, and raw materials cost is very cheap, have reduce cost, changing waste into resources and help advantage such as environment protection, become the focus of new super absorbent resin research and development in recent years.Microwave radiation promotes that the chemical reaction technology is a kind of emerging macromolecule synthesising technology, and traditional method incomparable advantage is arranged: it can shorten the reaction times greatly, enhances productivity; Do not have thermograde in the reaction process, reaction evenly also can suppress production of by-products; Microwave technology also can be used for dry reaction or half-dried reaction, can not pollute environment in building-up process.Microwave technology is used for the cellulose base High hydrophilous resin is synthetic not to appear in the newspapers.
Summary of the invention: the purpose of this invention is to provide a kind of High hydrophilous resin synthetic method, it can obviously shorten synthesising reacting time under the prerequisite that guarantees product performance, the simple and control easily of processing condition can reduce production costs, three-waste free discharge meets the basic demand of process for cleanly preparing.The present invention realizes by following proposal: a kind of microwave radiation cellulose base High hydrophilous resin synthetic method, it is achieved by following step: (one) gets the Mierocrystalline cellulose after 0.1g pulverizes, it is wetting to add 6～10mL deionized water, and gelatinization is 4～7 minutes under the microwave radiation of 300W～500W power; (2) take out the gelatinization thing, the content that adds 0.5mL～0.7mL is that the Potassium Persulphate of 0.01～0.03g/L or the content of potassium permanganate solution and 0.3～0.5mL are that the Sulfothiorine of 1.3～2.0g/L or the redox initiation system of sodium sulfite aqueous solution stir evenly, and causes under the microwave radiation of 80～150W power 4～7 minutes then; (3) content that adds successively again as linking agent is the N of 0.01～0.03g/L, N～methylene-bisacrylamide, epoxy chloropropane or polyoxyethylene glycol double methacrylate 1～2mL aqueous solution, acrylamide or sodium allylsulfonate 3～4g, acrylic or methacrylic acid 0.8～1.3mL, regulating degree of neutralization is 65%～75%, stirs evenly the back and reacts under the microwave radiation of 300～400W power 7～10 minutes; (4) place methyl alcohol to soak 3～5 hours the white product that generates, oven dry, pulverizing promptly get the cellulose base High hydrophilous resin.Adopt microwave to promote the synthetic chemistry reaction technology; based on the Graft Copolymerization of Cellulose reaction; select the novel redox catalyst/initiator system, under inert-free gas protection and condition of normal pressure, react, set up microwave radiation cellulose base High hydrophilous resin new synthetic process.Examine or check the influence to the product water-intake rate such as microwave irradiation power and time, grafted monomer and consumption, initiator system and consumption, linking agent kind and consumption, monomer degree of neutralization, obtained optimized process conditions.Under above-mentioned definite optimal conditions, only need tens minutes, just can finish cellulosic graft copolymerization, need tens hours relatively with the traditional method building-up reactions, improved the production efficiency of cellulose base High hydrophilous resin greatly; The test result of product being carried out salt tolerance, resistance to acids and bases and thermotolerance and water retention property shows that the water-intake rate of present method synthetic product can be up to 1200g/g, and absorption salt ratio can reach 158g/g, and has well lasting water retention capacity, is better than the bibliographical information result.Equipment required for the present invention is simple, and is easy to operate, and control easily is convenient to promote.This technology had both realized the cellulosic high added value development and use of renewable resources, had realized the environmental protectionization of synthesis technique again.
Embodiment one: it is achieved by following step: (one) gets the Mierocrystalline cellulose after 0.1g pulverizes, and adding 6～10mL deionization is wetting, and gelatinization is 4～7 minutes under the microwave radiation of 300W～500W power; (2) take out the gelatinization thing, the content that adds 0.5mL～0.7mL is that the Potassium Persulphate of 0.01～0.03g/L or the content of potassium permanganate solution and 0.3～0.5mL are that the Sulfothiorine of 1.3～2.0gL or the redox initiation system of sodium sulfite aqueous solution stir evenly, and causes under the microwave radiation of 80～150W power 4～7 minutes then; (3) content that adds successively again as linking agent is the N of 0.01～0.03g/L, N～methylene-bisacrylamide, epoxy chloropropane or polyoxyethylene glycol double methacrylate 1～2mL aqueous solution, acrylamide or sodium allylsulfonate 3～4g, acrylic or methacrylic acid 0.8～1.3mL, regulating degree of neutralization is 65%～75%, stirs evenly the back and reacts under the microwave radiation of 300～400W power 7～10 minutes; (4) place methyl alcohol to soak 3～5 hours the white product that generates, oven dry, pulverizing promptly get the cellulose base High hydrophilous resin.
Embodiment two: it is achieved by following step: (one) gets the Mierocrystalline cellulose after 0.1g pulverizes, and adding 6～8mL deionization is wetting, and gelatinization is 4～5 minutes under the microwave radiation of 300W～400W power; (2) take out the gelatinization thing, the content that adds 0.5mL～0.6mL is that the Potassium Persulphate of 0.01～0.03g/L or the content of potassium permanganate solution and 0.3～0.4mL are that the Sulfothiorine of 1.3～2.0gL or the redox initiation system of sodium sulfite aqueous solution stir evenly, and causes under the microwave radiation of 80～110W power 4～5 minutes then; (3) content that adds successively again as linking agent is the N of 0.01～0.03g/L, N～methylene-bisacrylamide, epoxy chloropropane or polyoxyethylene glycol double methacrylate 1～1.5mL aqueous solution, acrylamide or sodium allylsulfonate 3～3.5g, acrylic or methacrylic acid 0.8～1.1mL, regulating degree of neutralization is 65%～75%, stirs evenly the back and reacts under the microwave radiation of 300～350W power 7～8 minutes; (4) place methyl alcohol to soak 3～4 hours the white product that generates, oven dry, pulverizing promptly get the cellulose base High hydrophilous resin.
Embodiment three: it is achieved by following step: (one) gets the Mierocrystalline cellulose after 0.1g pulverizes, and adding 8.1～10mL deionization is wetting, and gelatinization is 6～7 minutes under the microwave radiation of 410W～500W power; (2) take out the gelatinization thing, the content that adds 0.65mL～0.7mL is that the Potassium Persulphate of 0.01～0.03g/L or the content of potassium permanganate solution and 0.43～0.5mL are that the Sulfothiorine of 1.3～2.0gL or the redox initiation system of sodium sulfite aqueous solution stir evenly, and causes under the microwave radiation of 120～150W power 6～7 minutes then; (3) content that adds successively again as linking agent is the N of 0.01～0.03g/L, N～methylene-bisacrylamide, epoxy chloropropane or polyoxyethylene glycol double methacrylate 1.6～2mL aqueous solution, acrylamide or sodium allylsulfonate 3.6～4g, acrylic or methacrylic acid 1.2～1.3mL, regulating degree of neutralization is 65%～75%, stirs evenly the back and reacts under the microwave radiation of 360～400W power 9～10 minutes; (4) place methyl alcohol to soak 4.5～5 hours the white product that generates, oven dry, pulverizing promptly get the cellulose base High hydrophilous resin.
Embodiment four: it is achieved by following step: (one) gets the Mierocrystalline cellulose after 0.1g pulverizes, and adding 8mL deionization is wetting, and gelatinization is 5 minutes under the microwave radiation of 360W power; (2) take out the gelatinization thing, the content that adds 0.6mL is that the Potassium Persulphate of 0.02g/L or the content of potassium permanganate solution and 0.4mL are that the Sulfothiorine of 1.6gL or the redox initiation system of sodium sulfite aqueous solution stir evenly, and causes 5 minutes under the microwave radiation of 100W power then; (3) content that adds successively again as linking agent is the N of 0.02g/L, N～methylene-bisacrylamide, epoxy chloropropane or the polyoxyethylene glycol double methacrylate 1.5mL aqueous solution, acrylamide or sodium allylsulfonate 3.5g, acrylic or methacrylic acid 1.0mL, regulating degree of neutralization is 70%, stirs evenly the back and reacts 8 minutes under the microwave radiation of 360W power; (4) place methyl alcohol to soak 4 hours the white product that generates, oven dry, pulverizing promptly get the cellulose base High hydrophilous resin.
Claims (4)
1, a kind of microwave radiation cellulose base High hydrophilous resin synthetic method, it is characterized in that it is achieved by following step: (one) gets the Mierocrystalline cellulose after 0.1g pulverizes, it is wetting to add 6～10mL deionized water, and gelatinization is 4～7 minutes under the microwave radiation of 300W～500W power; (2) take out the gelatinization thing, the content that adds 0.5mL～0.7mL is that the Potassium Persulphate of 0.01～0.03g/L or the content of potassium permanganate solution and 0.3～0.5mL are that the Sulfothiorine of 1.3～2.0g/L or the redox initiation system of sodium sulfite aqueous solution stir evenly, and causes under the microwave radiation of 80～150W power 4～7 minutes then; (3) content that adds successively again as linking agent is the N of 0.01～0.03g/L, N～methylene-bisacrylamide, epoxy chloropropane or polyoxyethylene glycol double methacrylate 1～2mL aqueous solution, acrylamide or sodium allylsulfonate 3～4g, acrylic or methacrylic acid 0.8～1.3mL, regulating degree of neutralization is 65%～75%, stirs evenly the back and reacts under the microwave radiation of 300～400W power 7～10 minutes; (4) place methyl alcohol to soak 3～5 hours the white product that generates, oven dry, pulverizing promptly get the cellulose base High hydrophilous resin.
2, microwave radiation cellulose base High hydrophilous resin synthetic method according to claim 1, it is characterized in that it is achieved by following step: (one) gets the Mierocrystalline cellulose after 0.1g pulverizes, it is wetting to add 6～8mL deionization, and gelatinization is 4～5 minutes under the microwave radiation of 300W～400W power; (2) take out the gelatinization thing, the content that adds 0.5mL～0.6mL is that the Potassium Persulphate of 0.01～0.03g/L or the content of potassium permanganate solution and 0.3～0.4mL are that the Sulfothiorine of 1.3～2.0gL or the redox initiation system of sodium sulfite aqueous solution stir evenly, and causes under the microwave radiation of 80～110W power 4～5 minutes then; (3) content that adds successively again as linking agent is the N of 0.01～0.03g/L, N～methylene-bisacrylamide, epoxy chloropropane or polyoxyethylene glycol double methacrylate 1～1.5mL aqueous solution, acrylamide or sodium allylsulfonate 3～3.5g, acrylic or methacrylic acid 0.8～1.1mL, regulating degree of neutralization is 65%～75%, stirs evenly the back and reacts under the microwave radiation of 300～350W power 7～8 minutes; (4) place methyl alcohol to soak 3～4 hours the white product that generates, oven dry, pulverizing promptly get the cellulose base High hydrophilous resin.
3, microwave radiation cellulose base High hydrophilous resin synthetic method according to claim 1, it is characterized in that it is achieved by following step: (one) gets the Mierocrystalline cellulose after 0.1g pulverizes, it is wetting to add 8.1～10mL deionization, and gelatinization is 6～7 minutes under the microwave radiation of 410W～500W power; (2) take out the gelatinization thing, the content that adds 0.65mL～0.7mL is that the Potassium Persulphate of 0.01～0.03g/L or the content of potassium permanganate solution and 0.43～0.5mL are that the Sulfothiorine of 1.3～2.0gL or the redox initiation system of sodium sulfite aqueous solution stir evenly, and causes under the microwave radiation of 120～150W power 6～7 minutes then; (3) content that adds successively again as linking agent is the N of 0.01～0.03g/L, N～methylene-bisacrylamide, epoxy chloropropane or polyoxyethylene glycol double methacrylate 1.6～2mL aqueous solution, acrylamide or sodium allylsulfonate 3.6～4g, acrylic or methacrylic acid 1.2～1.3mL, regulating degree of neutralization is 65%～75%, stirs evenly the back and reacts under the microwave radiation of 360～400W power 9～10 minutes; (4) place methyl alcohol to soak 4.5～5 hours the white product that generates, oven dry, pulverizing promptly get the cellulose base High hydrophilous resin.
4, microwave radiation cellulose base High hydrophilous resin synthetic method according to claim 1, it is characterized in that it is achieved by following step: (one) gets the Mierocrystalline cellulose after 0.1g pulverizes, it is wetting to add the 8mL deionization, and gelatinization is 5 minutes under the microwave radiation of 360W power; (2) take out the gelatinization thing, the content that adds 0.6mL is that the Potassium Persulphate of 0.02g/L or the content of potassium permanganate solution and 0.4mL are that the Sulfothiorine of 1.6gL or the redox initiation system of sodium sulfite aqueous solution stir evenly, and causes 5 minutes under the microwave radiation of 100W power then; (3) content that adds successively again as linking agent is the N of 0.02g/L, N～methylene-bisacrylamide, epoxy chloropropane or the polyoxyethylene glycol double methacrylate 1.5mL aqueous solution, acrylamide or sodium allylsulfonate 3.5g, acrylic or methacrylic acid 1.0mL, regulating degree of neutralization is 70%, stirs evenly the back and reacts 8 minutes under the microwave radiation of 360W power; (4) place methyl alcohol to soak 4 hours the white product that generates, oven dry, pulverizing promptly get the cellulose base High hydrophilous resin.
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| CN101173157B (en) * | 2007-10-15 | 2010-06-02 | 东北林业大学 | Water-loss reducer using waste pouce or Chinese medicine slag and wastepaper as raw material, and production method thereof |
| CN102153665A (en) * | 2011-03-11 | 2011-08-17 | 陕西农产品加工技术研究院 | Method for preparing high water absorbing gel by using apple residues as raw materials |
| CN102190762A (en) * | 2011-03-07 | 2011-09-21 | 万富 | Method for preparing water retention agent from bagasse |
| CN103936096A (en) * | 2014-04-21 | 2014-07-23 | 青岛理工大学 | Method for degrading perfluorocarboxylic acid pollutants by microwave radiation |
| CN104140506A (en) * | 2014-07-18 | 2014-11-12 | 武汉理工大学 | Palm fiber stem grafting ternary polymerization high-salt-resistance water-absorbent resin and preparing method thereof |
| CN105524283A (en) * | 2016-01-05 | 2016-04-27 | 华南理工大学 | Hemicellulose based water absorption and retention material and preparation method therefor |
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| CN108017765A (en) * | 2017-12-05 | 2018-05-11 | 华南理工大学 | A kind of Chinese medicine dreg fiber base resin and its preparation and application |
| CN108623748A (en) * | 2018-05-24 | 2018-10-09 | 中国农业大学 | A kind of load boron fibre element super absorbent resin and preparation method thereof |
| WO2021208062A1 (en) * | 2020-04-17 | 2021-10-21 | 华南理工大学 | Dynamically covalently cross-linked cellulose-based bioplastic, wood-plastic composite material, preparation method therefor, and use thereof |
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2003
- 2003-12-23 CN CN 200310107773 patent/CN1250630C/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101173157B (en) * | 2007-10-15 | 2010-06-02 | 东北林业大学 | Water-loss reducer using waste pouce or Chinese medicine slag and wastepaper as raw material, and production method thereof |
| CN102190762A (en) * | 2011-03-07 | 2011-09-21 | 万富 | Method for preparing water retention agent from bagasse |
| CN102153665A (en) * | 2011-03-11 | 2011-08-17 | 陕西农产品加工技术研究院 | Method for preparing high water absorbing gel by using apple residues as raw materials |
| CN102153665B (en) * | 2011-03-11 | 2012-06-27 | 陕西农产品加工技术研究院 | Method for preparing high water absorbing gel by using apple residues as raw materials |
| CN103936096A (en) * | 2014-04-21 | 2014-07-23 | 青岛理工大学 | Method for degrading perfluorocarboxylic acid pollutants by microwave radiation |
| CN103936096B (en) * | 2014-04-21 | 2015-05-13 | 青岛理工大学 | Method for degrading perfluorocarboxylic acid pollutants by microwave radiation |
| CN104140506A (en) * | 2014-07-18 | 2014-11-12 | 武汉理工大学 | Palm fiber stem grafting ternary polymerization high-salt-resistance water-absorbent resin and preparing method thereof |
| CN105524283B (en) * | 2016-01-05 | 2018-06-22 | 华南理工大学 | A kind of hemicellulose group water-absorbing-retaining material and preparation method thereof |
| CN105524283A (en) * | 2016-01-05 | 2016-04-27 | 华南理工大学 | Hemicellulose based water absorption and retention material and preparation method therefor |
| CN107828379A (en) * | 2017-11-13 | 2018-03-23 | 陕西科技大学 | A kind of humic acid drop haze dust suppressant and its preparation method and application |
| CN107828379B (en) * | 2017-11-13 | 2020-06-02 | 陕西科技大学 | Humic acid haze-reducing dust suppressant and preparation method and application thereof |
| CN108017765A (en) * | 2017-12-05 | 2018-05-11 | 华南理工大学 | A kind of Chinese medicine dreg fiber base resin and its preparation and application |
| CN108017765B (en) * | 2017-12-05 | 2019-10-18 | 华南理工大学 | A kind of Chinese medicine dreg fiber base resin and its preparation and application |
| CN108623748A (en) * | 2018-05-24 | 2018-10-09 | 中国农业大学 | A kind of load boron fibre element super absorbent resin and preparation method thereof |
| CN108623748B (en) * | 2018-05-24 | 2020-06-12 | 中国农业大学 | Boron-loaded cellulose super absorbent resin and preparation method thereof |
| WO2021208062A1 (en) * | 2020-04-17 | 2021-10-21 | 华南理工大学 | Dynamically covalently cross-linked cellulose-based bioplastic, wood-plastic composite material, preparation method therefor, and use thereof |
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